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EP0817803B1 - Verfahren zur aktivierung von polysacchariden, danach hergestellte polysaccharide und deren verwendung - Google Patents

Verfahren zur aktivierung von polysacchariden, danach hergestellte polysaccharide und deren verwendung Download PDF

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Publication number
EP0817803B1
EP0817803B1 EP96908120A EP96908120A EP0817803B1 EP 0817803 B1 EP0817803 B1 EP 0817803B1 EP 96908120 A EP96908120 A EP 96908120A EP 96908120 A EP96908120 A EP 96908120A EP 0817803 B1 EP0817803 B1 EP 0817803B1
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EP
European Patent Office
Prior art keywords
cellulose
polysaccharide
ammonia
liquid ammonia
pressure
Prior art date
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EP96908120A
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German (de)
English (en)
French (fr)
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EP0817803A1 (de
Inventor
Ties Karstens
Hans Steinmeier
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Cerdia Produktions GmbH
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Rhodia Acetow GmbH
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/06—Rendering cellulose suitable for etherification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
    • C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
    • C08B37/0096—Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives

Definitions

  • the invention relates to a method for activating polysaccharides, in which the polysaccharide starting material with liquid ammonia at one opposite Atmospheric pressure increased outlet pressure and at a temperature of at least about 25 ° C is contacted, the amount of liquid ammonia at least for wetting the surface of the polysaccharide starting material sufficient, and then relaxed, as well as activated manufactured afterwards Polysaccharides.
  • Cellulose is a linear polysaccharide made up of glucose monomer units.
  • the smallest macroscopic structural element of native cellulose are elementary crystallites, which consist of cellulose molecules assembled in parallel. Because of the macromolecular nature of the molecules, many of them are Elemental crystallites over disordered molecular segments to long strands, the Elementary fibrils, linked. These elementary fibrils can vary along a Gather length to secondary aggregations. The length of the secondary aggregations and the degree of aggregation are important structural features.
  • Ammonia-cellulose complexes are formed.
  • the trained Ammonia-cellulose complexes are relatively unstable. When evaporating the Ammoniaks returns three times the increase in fiber diameter to his Initial dimensions back. The complex will also be destroyed if that Ammonia is washed out with water or alcohol. Here, too, becomes regular regained the original cellulose crystal structure.
  • DE 43 29 937 proposes to maintain the activation state after the Ammonia swelling before, the necessary remaining ammonia under the influence of replace superheated steam with water as a swelling or inclusion agent. It has been shown that the activation state is quickly lost when that material treated in this way is not immediately processed.
  • DE 0 108 991 the cellulose becomes deeper after swelling in liquid ammonia Temperature is not recovered in a dry form, but the mixture is with aqueous alkali hydroxide solution and the ammonia in the presence of Alkalizing agent removed. The alkaline cellulose suspension obtained is immediately subjected to an etherification reaction.
  • One aim of the method according to the invention described below is, inter alia, therefore to provide a process product from which the residual ammonia can be used without problems can be largely removed while maintaining the activation without additional Inclusion agents, such as Water, are required.
  • US-A-5 322 524 describes cellulose fibers or cellulose-containing fibers improved resistance to abrasion and with increased permeability towards chemicals.
  • the increased permeability leads to an improved Chemical activity.
  • the fibers of crystalline cellulose III obtained can treated in ethylenediamine and then cooked in dimethylformamide to give the To convert cellulose III into cellulose IV.
  • the stability of cellulose III will demonstrated that they are not in cellulose when boiled in water for one hour I is transferable. It is characterized by a specific X-ray diffraction spectrum with peaks at diffraction angles 2 ⁇ of 11.5, 15.5 and 20.5.
  • the above State of the art described largely corresponds to that according to the literature reference "Textile Research Journal", July 1986, pp. 419-424.
  • EP-A-0 077 287 relates to the use of liquid ammonia for activation of cellulose contained in animal feed using increased pressure. Thereafter, the cellulose-containing material is liquid at high pressure Treated ammonia. Then the pressure is quickly reduced to Atmospheric pressure, which leads to a boiling of ammonia and a fibrillation of the Cellulose material leads. The cellulose raw material remains in the system, whose internal pressure is reduced to atmospheric pressure.
  • US 3,707,436 proposes a process for making pulp for the Paper production, in which lignocellulosic material with anhydrous ammonia in an enclosed space is impregnated under pressure and the pressure suddenly is reduced, with an explosive removal of ammonia and a The material is ejected.
  • the starting material are preferred Wood chips in which, in addition to cellulose, considerable amounts of lignin, hemicellulose and up to 100% water content.
  • the wood chips come with so much Ammonia impregnates that in the system at least the same amount of ammonia as is present in water and warmed to a temperature necessary for its plasticization is sufficient.
  • a mass ratio of ammonia to Water used in the range of 2 to 4.
  • the hemicelluloses remain insoluble in water Shape in the process product, they make the material plastic and lend it paper products made from strength.
  • the cellulose obtained is slightly more amorphous and plastic than in the initial state.
  • US 5 171 592 describes a method for the treatment of biomass.
  • the process includes the "Ammonia Freeze Explosion” (AFEX), on biomass swollen with liquid ammonia and then opened by opening a valve a flash container is detonated. In the explosion, about 25% of the used ammonia evaporates.
  • the biomass is preferably passed through Treat with pre-dried ammonia vapor, deaerated and preheated. After the AFEX treatment, the remaining liquid ammonia is removed Expelled treatment with ammonia vapor.
  • cellulose In wood and other biomass, cellulose is associated with lignin and Hemicelluloses before. Biomass usually also contains at least 50% Humidity. Lignin is a complex, highly polymeric natural product that is incorporated into the interfibrillary capillary spaces of the cellulose fibers is embedded. The fibrillaries Cellulose chains are covered with lignin and hemicellulose via a thin, cross-linked layer other fibrils connected to a fiber bundle. The matrix of lignin and Hemicellulose surrounds and protects the cellulose fibrils and keeps the structure similar like a resin in a fiberglass composite.
  • the invention has for its object a method of the aforementioned To propose the type of process product compared to the comparative products of the State of the art in the usual derivatization methods an improved Has activity, e.g. in acylation, alkylation, silylation, xanthogenation and carbamoylation.
  • the residual ammonia content of the process product should can be reduced to less than 0.2 mass% while maintaining the activity.
  • this object is achieved by a method which thereby is characterized in that the polysaccharide / liquid ammonia system is available standing volume explosively while lowering the pressure by at least 5 bar is enlarged.
  • the explosion-like increase in volume preferably takes place within one Time of less than one second, especially less than 0.5 seconds.
  • Amount of polysaccharide / liquid ammonia turned off.
  • the polysaccharide starting material and the liquid ammonia are preferably in a printing device contacted and the system polysaccharide / liquid ammonia by transferring it into an explosion space opposite the pressure device relaxed larger volume.
  • the outlet pressure is preferably between about 5 and 46 bar and in particular between about 25 and 30 bar. The minimum pressure drop of 5 bar is critical. If it falls below, then the goal of the invention is not reached, i.e. the desirable properties of the process product do not arise on.
  • the upper limit of about 46 bar results in his Advantages not exceeded. His attitude requires one relatively large expenditure on equipment, so that a further increase under practical Considerations does not make sense.
  • the Output pressure in the polysaccharide / liquid ammonia system explosively lowered at least about 10 bar and in particular about 30 bar.
  • a sufficient amount of ammonia must be injected into the printing device. so that under the pressure or temperature conditions required according to the invention liquid ammonia is present and at least the surface of the Polysaccharide starting material is wetted.
  • Preferably 1 part by mass Polysaccharide at least about 1 part by mass of liquid ammonia, in particular at least about 5 parts by weight and most preferably about 5 to 10 parts by weight liquid ammonia. At least one is caused by the action of the ammonia partial swelling of the polysaccharide starting material.
  • polysaccharides can be activated by the process according to the invention. They are preferably polysaccharides which have crystalline regions due to the formation of more intermolecular hydrogen bonds. Such polysaccharides are generally not or only sparingly soluble in cold water.
  • the polysaccharides can be modified by derivatization, crosslinking or conversion.
  • the polysaccharides used preferably have a polyhexose backbone, ie a backbone whose monomers are C 6 saccharides. These include the biopolymers starch, cellulose, inulin, chitin and alginic acid, of which cellulose, chitin and starch are preferred.
  • polysaccharides mentioned each contain only one type of building block - albeit possibly in alternating glycosidic linkage - and are therefore to be counted as homoglycans.
  • Polysaccharides which can also be activated according to the invention are, in addition, heteroglycans composed of various monomer units.
  • the preferred heteroglycans include the galactomannans, of which guar gum is particularly preferred.
  • the polysaccharides used preferably have a degree of polymerization DP (average number of monomer units bound in the macromolecule) of 500 to 10,000, in particular from 500 to 3,000, but never less than 150.
  • degree of polymerization DP average number of monomer units bound in the macromolecule
  • a particularly suitable cellulosic starting material for carrying out the process according to the invention are chemical pulps in rolls or bales with a density of about 0.6 to 0.8 g / cm 3 .
  • the polysaccharides used according to the invention are preferably chemically pure in front. They preferably contain less than 18% by mass, in particular less than 9 % By mass, foreign substances, such as in particular proteins and lignin. Especially preferred embodiments contain the polysaccharides less than 5, in particular less than 1 mass%, foreign substances. As a rule, the used polysaccharides be protein-free. Too high a protein content leads to that undesirable side reactions occur during further processing.
  • the degree of activation achievable according to the invention depends on the water content of the Polysaccharide starting material. A too high water content leads to insufficient Activation, probably due to the thinning effect of the water molecules the ammonia is due.
  • the water content of the polysaccharide starting material is therefore preferably less than 12% by mass, in particular less than about 9% by mass. In particularly preferred embodiments, the Water content less than 0.5% by mass. Because most polysaccharides are hygroscopic and can absorb water during storage at ambient conditions it may be necessary to maintain a low water or moisture content, subject the polysaccharide starting material to suitable drying steps. The equilibrium water content of most polysaccharides under normal conditions is about 7 to 9 mass%.
  • the polysaccharide starting material and an amount of n ammonia are at a pressure p 1 and a temperature T 1 ( ⁇ about 25 ° C.) in a volume V 1 at the beginning of the process.
  • the fraction ⁇ • n is in liquid form under these conditions.
  • Additional inert gas pressure can bring ⁇ close to 1 and raise p 1 .
  • This system is subjected to a change in state while increasing the volume to V 2 , the new temperature T 2 and the new pressure p 2 being established and (p 1 -p 2 ) ⁇ 5 bar.
  • This change is essentially adiabatic, but energy could also be added to the system at the same time, for example by heating the explosion chamber.
  • V 2 , p 2 , T 2 there is preferably more than about 50%, in particular more than 80%, of the originally liquid amount of ammonia ⁇ • n in gaseous form. An almost complete, sudden evaporation of the liquid ammonia is most preferred. Since the adiabatic change in state is accompanied by a decrease in temperature, T 1 must be chosen sufficiently high and / or p 2 sufficiently low to meet this condition. In order to achieve the greatest possible pressure drop for a given volume difference (V 2 -V 1 ), the explosion chamber is kept under vacuum before introducing the polysaccharide / liquid ammonia system when the process is carried out discontinuously. If the process is carried out continuously, gaseous ammonia is preferably continuously withdrawn from the explosion space in order to maintain a sufficiently low pressure.
  • the inventive method in which the amount of liquid Ammonia suddenly increased to more than by volume increase / decrease in pressure 50% vaporized differs from the "ammonia explosion" process the state of the art.
  • the known methods is usually by opening one Valve causes a pressure drop on an autoclave. This evaporates quickly a small amount of the ammonia used, for example 20%, and the mass treated with liquid ammonia remains with the remaining ammonia in the autoclave. Due to the cooling effect that occurs, it shatters and breaks the mass. The remaining amount of liquid ammonia is there continuously boiling, the vaporization of the ammonia takes place over you long period.
  • the residual ammonia content is primary process product quite high, generally significantly larger than 1 Dimensions-%.
  • the process according to the invention can be carried out batchwise or continuously be performed.
  • the apparatus has essentially a pressure vessel that fills with the material to be treated and a collecting or Expansion tank on. It is important to note that the valve is in the open position Condition has a large clear opening, so that during the explosion process Polysaccharide starting material does not jam and not only ammonia escapes.
  • the expansion tank has a multiple volume compared to the pressure tank on, for example, the volume of the pressure vessel is 1 l and the volume of the Expansion tank 30 l.
  • the pressure vessel is with a supply line for Ammonia, optionally with the interposition of a pressure-increasing device, connected. To further increase the pressure, a supply line for Inert gases, e.g. Nitrogen. be provided.
  • the process could be done using a pipe or tube cylindrical, pressure-resistant reactor are carried out, in which the Contacting polysaccharide and liquid ammonia in the cylinder of the Reactor takes place and the impregnated material with the help of a screw conveyor as Graft is transported through the reactor and intermittently through a valve or a suitable system of pressure locks is discharged into a collecting room becomes.
  • Suitable components that the person skilled in the art can easily carry out of the method according to the invention can be found in EP-A-329 173 and of U.S. 4,211,163.
  • the contact time between the liquid ammonia and the starting material inside the pressure vessel is not critical. It can be very short, for example few seconds. A reasonable time frame can be around 1 s to 60 min with polysaccharides that are difficult to swell, but also significantly longer. The For practical reasons, a contact time of less than 1 s can hardly be achieved. A treatment of longer than about 60 minutes usually does not lead to any further treatment technical advantage. Contact times in the range from 10 s to 1 min are in generally preferred.
  • the polysaccharide is preferred subjected to heat treatment and / or vacuum treatment in order to Reduce residual water and ammonia.
  • Optimal results will be for example at a temperature of 60 ° C and a pressure of 10 mbar over 2 h reached.
  • the residual water content can be below 1% by mass and Residual ammonia content can be reduced to below 0.2% by mass.
  • cellulose has one Spatial network structure in which the elementary fibrils extend over a certain length fibrillar aggregates are associated.
  • the degree of aggregation and the aggregation length are important structural features.
  • the easiest way to determine the Length of these elements in cellulose fibers is the course of the heterogeneous to investigate hydrolytic degradation. Due to the tight packing of the Cellulose molecules in the elementary crystallites or fused aggregates of the Elementary fibrils is the heterogeneous hydrolytic attack by acid or more less on the surface molecules of the elementary fibrils or their aggregations and delimits the disordered segments of the cellulose macromolecules that combine the crystallites into fibrillar strands.
  • An activated cellulose obtained according to the invention is in the form of fluff.
  • This is characterized by the fact that he is responsible for the various derivatization measures has an advantageous LODP value. This is preferably between about 50 and 200, in particular between about 100 and 160 and very particularly preferred between about 120 to 145.
  • the addressed framework of LODP values that preferred configurations of the invention are an indication of the improved accessibility of the fluff according to the invention for example Derivatization reagents.
  • the cellulose fluff according to the invention is also characterized by a previously unattained low density of less than about 0.2 g / cm 3 . This is one reason for his particular activity in the derivatization processes mentioned. This advantage is increased if the density of the down is less than 0.1 g / cm 3 . It is a special measure here and provides information about the extent of the explosion treatment.
  • the particularly high activity in the various derivatization processes goes mainly due to the fact that the fluff or the fibers forming it for the chemicals used are more accessible. This leads to lower ones Response times and less chemicals. Further fall more homogeneous derivatization products.
  • acylation e.g. Acetylation, Silylation, xanthation or production of carbamates and Alkylation by etherification with alkyl halides, epoxy compounds, unsaturated organic compound (Michael addition) and the like.
  • suitable chemicals e.g. in morpholine N-oxide. This is a well-known solvent for cellulose, for example Spinning solution.
  • a cellulose activated according to the invention is characterized in that it has an X-ray diffraction spectrum with peaks of the specified relative intensities at the following diffraction angles 2 ⁇ and with the relative intensities: Peak 11.25 ⁇ 1 relative intensity from about 15 to 25; Peak 17 ⁇ 1 of relative intensity from about 25 to 40; Peak 20.5 ⁇ 1 of the relative intensity 100 (reference value).
  • This X-ray spectrum is clearly different from the X-ray spectra of the known cellulose modifications I, II, III and IV. A new cellulose modification is therefore accessible through the method according to the invention.
  • a special feature of the cellulose fluff according to the invention is in Differentiation from the prior art described in the introduction in that it when boiling in water at atmospheric pressure for at least one hour is largely converted back into cellulose I. This is strictly Contrary to the statements of US-A-5 322 524 about what is described therein Material.
  • ammonia content of the cellulose fluff according to the invention is about 0.5% by mass.
  • the cellulose fluff according to the invention is also characterized in that it has a desirably low water content of less than about 6% by mass, in particular less than 1% by mass can be produced.
  • a desirably low water content of less than about 6% by mass, in particular less than 1% by mass can be produced.
  • the water content at the practical implementation of the teaching according to the invention easily below the value be reduced, which have commercially available cellulose materials. These contain regularly about 6 to 7% water. If the consumer is offered a material whose water content is below 1% by mass in particular, this means a Reduction of transport costs and a significant reduction in the amount of chemicals at e.g. of acylation.
  • the method according to the invention is also used for activation of guar gum.
  • Guar gum activated according to the invention and from it by derivatization Connections produced stand out when used as a thickener e.g. by advantageous rheological properties. Aqueous solutions of this In contrast to untreated forms, they largely show a shear effect independent constant viscosity. Guar gum derivatives before derivatization activated according to the invention also show favorable redispersibility after drying, what happens when textile printing using thickened color pastes is an advantage.
  • the method according to the invention is also used in the activation of Chitin.
  • Chitin is usually present in smooth, hard particles, in solvents are extremely difficult to dissolve.
  • the treatment according to the invention takes place morphological change while roughening the surface and widening the Particles instead. Accessibility to chemicals and / or solvents becomes critical improved.
  • Chitin activated according to the invention can be obtained via a partial deacetylation to chitosan interesting and so far difficult to access Products for cosmetic, medical, food technology applications and manufacture chemical-technical area.
  • the complete “explosion” causes a polysaccharide / liquid system at least wetted with liquid ammonia Ammonia in an explosion space a product in about a second if possible obtained, which is characterized by particularly advantageous properties. It points an unusually low density. Among other things, this favors the derivatizations, for example in the context of alkylation, acylation, silylation and Xanthation, since the polysaccharides activated according to the invention are better for Derivatives are accessible. This reduces the response time and the effort of chemicals. One reason for the improved reactivity can also be found in the chemical-structural Special features of the products according to the invention lie.
  • Determination of the level-off-DP of cellulose 590 ml of denatured ethyl alcohol are mixed with 30 ml of concentrated sulfuric acid and heated under reflux on the water bath for 30 minutes. After cooling, the sulfuric acid content is determined to check, which should be approximately 5.8%. 500 mg of the cellulose sample to be examined are heated to boiling (82 ° C.) with 30 ml of the ethanolic sulfuric acid in a 100 ml round-bottom flask provided with a reflux condenser for 7 hours. The cellulose is then separated from the ethanolic sulfuric acid on a frit, washed first with water and finally with ethanol, and the DP of the dried, hydrolytically degraded cellulose is determined.
  • the DP value was determined using the Cuoxam method.
  • Acetylation test This test examines the temperature profile during the acetylation of cellulose samples. The following procedure was used: 800 g of acetic acid and 1.0 ml of sulfuric acid, which had previously been heated to 70 ° C, were added to 200 g of the cellulose to be investigated in a 2 l flask and on a heated roller bench at 45 to 50 ° C kept. After about 1.5 hours, the melting point of the acetic acid is determined and the amount of acetic anhydride required for drying is calculated. After a further 30 min at 45 to 50 ° C, the calculated amount of anhydride is added and the mixture is cooled to 20 to 22 ° C.
  • the mixture is mixed with 500 ml of acetic anhydride in a Dewar vessel with constant stirring. From the time of the anhydride addition, the temperature change is recorded with an XY recorder depending on the time. The determination ends when the temperature begins to drop.
  • Example 1 This example illustrates the activation of cellulose according to the invention in a batch process.
  • the ammonia content of the product in the explosion room was around 1 % By weight, based on the defibrillated pulp.
  • the gaseous ammonia was isolated to isolate the process product Applying a vacuum, which leads to a reduction in the ammonia content led to 0.2 mass%.
  • DP and LODP values were as follows: DP LODP Before treatment with ammonia 1,025 349 After treatment with ammonia 975 148
  • Example 2 In this example, the duration of the pressure drop in an ammonia explosion according to the invention was investigated.
  • Example 3 X-ray spectra with Cu ⁇ radiation were recorded from cellulose samples activated according to the invention and from comparison samples, which are shown in FIG. 1.
  • Sample A is a cellulose activated as in Example 1. The residual ammonia content was less than 0.5% by mass. Sample B was subjected to a heat treatment and no longer contained any detectable residual ammonia content. Sample C was treated with water at 80 ° C for 60 minutes. Sample D is a comparative cellulose which was treated with aqueous ammonia solution (ratio of aqueous NH 3 / pulp 10: 1) and then dried. Comparative sample E is untreated cellulose.
  • Example 4 Chemical pulps which had been adjusted to different water contents were subjected to an ammonia explosion as in Example 1. The cellulose materials obtained were subjected to the acetylation test described above, commercial pulp was used as a reference. The temperature / time profiles are shown in FIG. 2. Samples F, G and H correspond to initial water contents of 30, 7 and 0.5 mass%, I is the reference.
  • Figure 2 also shows the influence of the initial water content on the activity of the received product recognizable.
  • the sample with the highest initial water content (30%) shows less activity.
  • the other two samples (with the Equilibrium moisture content of the pulp in an ambient atmosphere of 7% or 0.5% dried) react much faster, with samples G and H there is no significant difference.
  • Example 5 In this example, the behavior of pulp activated according to the invention during carboxymethylation or silylation with hexamethyldisilazane is investigated.
  • untreated pulp was the carboxymethylation process described above subject.
  • the product obtained was in Water swelled and dispersed.
  • the solution was cloudy and showed many unresolved Fibers.
  • Example 6 This example illustrates the activation of guar gum according to the invention.
  • guar gum 50 g guar gum (powdered, water content about 7.9%, protein content about 4%) were in an autoclave with a volume of 1 l with a double wall Steam heating given. Then 280 g of liquid ammonia were added The valve is pressed into the autoclave. By steam heating the autoclave the temperature was raised to 60 ° C. This resulted in a pressure of 30 bar. The system was held under these conditions for 30 minutes. Then was the guar gum / liquid ammonia system suddenly and completely into one Explosion container with a volume of 100 l relaxed. The water content was after the explosion 2.6%. The process product was collected and at 60 ° C dried. The residual ammonia content was 1% by mass.
  • FIG. 3 shows the viscosity curves (viscosity as a function of Shear rate, expressed as rpm) of a 1% solution in water carboxymethylating guar gums without pretreatment (K) and carboxymethylated ammonia-exploded guar gums (L).
  • the viscosity curve of the before the carboxymethylation of guar gums activated according to the invention proceeds clearly flatter than that of the comparative product. It has a much longer Newtonian Area on, i.e. the change in viscosity for small shear gradients is less than with the comparative product. The viscosity is clear at low shear rate smaller.
  • Example 7 This example shows the use of the carboxymethylated guar gum produced in Example 5 as a thickener in textile printing.
  • Textile printing involves thickening with carboxymethylated guar gum Dye paste is applied to the textile goods, then the textile goods steamed and the thickener washed out again. It turns out that the Comparative sample without pretreatment before carboxymethylation bad is washable. This leads to a hard grip on the textile goods. With that before ammonia-exploded and then carboxymethylated guar gum on the other hand, a problem-free washing out, the textile handle then is pleasantly soft.
  • Example 8 This example illustrates the activation of chitin according to the invention.
  • the originally very smooth and hard surface of the chitin particles expanded like a popcorn after the ammonia explosion and felt less smooth and hard.
  • the IR spectrum of the product obtained shows clear differences from the IR spectrum of the untreated chitin.
  • the intensity of the carbonyl vibration band in the acetyl group is significantly reduced. This clearly indicates that a considerable part of the chitin has been converted into chitosan by the action of ammonia.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Emergency Medicine (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
EP96908120A 1995-03-25 1996-03-22 Verfahren zur aktivierung von polysacchariden, danach hergestellte polysaccharide und deren verwendung Expired - Lifetime EP0817803B1 (de)

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DE19511061 1995-03-25
DE19511061 1995-03-25
PCT/EP1996/001274 WO1996030411A1 (de) 1995-03-25 1996-03-22 Verfahren zur aktivierung von polysacchariden, danach hergestellte polysaccharide und deren verwendung

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EP0817803B1 true EP0817803B1 (de) 1999-06-16

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EP (1) EP0817803B1 (pt)
JP (2) JP3390015B2 (pt)
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AT (1) ATE181338T1 (pt)
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HU (1) HUP9802337A3 (pt)
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CZ284387B6 (cs) 1998-11-11
WO1996030411A1 (de) 1996-10-03
BR9607992A (pt) 1999-11-30
ATE181338T1 (de) 1999-07-15
ES2135221T3 (es) 1999-10-16
CA2214245C (en) 2001-10-02
CN1083454C (zh) 2002-04-24
PL322468A1 (en) 1998-02-02
CZ300597A3 (en) 1997-12-17
KR100254840B1 (ko) 2000-05-01
ZA962370B (en) 1996-10-07
DE59602248D1 (de) 1999-07-22
US5939544A (en) 1999-08-17
KR19980703294A (ko) 1998-10-15
CN1179781A (zh) 1998-04-22
BG101888A (en) 1998-04-30
EP0817803A1 (de) 1998-01-14
CA2214245A1 (en) 1996-10-03
HUP9802337A2 (hu) 1999-02-01
HUP9802337A3 (en) 1999-03-29
MX9707309A (es) 1997-11-29
JPH10505130A (ja) 1998-05-19
AU5148196A (en) 1996-10-16
BG62778B1 (bg) 2000-07-31
DE19611416A1 (de) 1996-09-26
JP3390015B2 (ja) 2003-03-24
SK128597A3 (en) 1998-03-04
EA000169B1 (ru) 1998-10-29
AU695331B2 (en) 1998-08-13
EA199700268A1 (ru) 1998-02-26
JP2002161101A (ja) 2002-06-04

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